折点氯化法除钨冶炼厂氨氮废水研究
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摘要
钨冶炼过程中产生大量氨氮废水,直接排放对环境造成破坏。研究采用折点氯化法处理钨冶炼厂排放的氨氮废水,研究了反应时间、初始氨氮浓度、p H值、温度对于模拟废水的氨氮脱除效果的影响,以及折点氯化法工业化应用的效果。模拟氨氮废水试验结果表明,当pH值为11时,试验效果最好:在45 min后,反应到达折点,氨氮浓度降至5.3 mg·L~(-1),氯气利用率在95%左右。而温度和初始浓度两个因素对氨氮脱除无明显影响。折点氯化法工业试验结果表明:不同浓度(80~1 800 mg·L~(-1))的钨冶炼厂废水经过折点氯化法处理后,氨氮均能够降低到15 mg·L~(-1)以下,且到达折点时Cl_2与NH_3-N的质量比为7.8。
A large amount of ammonia-nitrogen wastewater is produced during the smelting process of tungsten, and the direct discharge of the wastewater causes damage to the environment. In this paper, we employed breakpoint chlorination to treat the ammonia nitrogen wastewater discharged from the tungsten smelter. Besides, the effects of reaction time, initial ammonia nitrogen concentration, pH value, the effect of temperature and stirring speed on the removal of ammonia nitrogen, and the effect of pH value and stirring speed on the utilization of chlorine gas were studied. The experimental results of simulated ammonia nitrogen wastewater showed that when the pH was 11, the experimental results were the best: after 45 minutes, the reaction reached the breakpoint, the ammonia nitrogen concentration dropped to 5.3 mg·L~(-1), and the chlorine gas utilization rate was about 95 %.The temperature and initial concentration had no significant effect on ammonia nitrogen removal. The experimental results of the breakpoint chlorination showed that the ammonia smelter wastewater with different concentrations(80~1800 mg·L~(-1)) could be reduced to below 15 mg·L~(-1) after the chlorination treatment. The mass ratio of Cl_2 to NH_3-N was 7.8 when the breakpoint was reached.
A large amount of ammonia-nitrogen wastewater is produced during the smelting process of tungsten, and the direct discharge of the wastewater causes damage to the environment. In this paper, we employed breakpoint chlorination to treat the ammonia nitrogen wastewater discharged from the tungsten smelter. Besides, the effects of reaction time, initial ammonia nitrogen concentration, pH value, the effect of temperature and stirring speed on the removal of ammonia nitrogen, and the effect of pH value and stirring speed on the utilization of chlorine gas were studied. The experimental results of simulated ammonia nitrogen wastewater showed that when the pH was 11, the experimental results were the best: after 45 minutes, the reaction reached the breakpoint, the ammonia nitrogen concentration dropped to 5.3 mg·L~(-1), and the chlorine gas utilization rate was about 95 %.The temperature and initial concentration had no significant effect on ammonia nitrogen removal. The experimental results of the breakpoint chlorination showed that the ammonia smelter wastewater with different concentrations(80~1800 mg·L~(-1)) could be reduced to below 15 mg·L~(-1) after the chlorination treatment. The mass ratio of Cl_2 to NH_3-N was 7.8 when the breakpoint was reached.
引文
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[19] WATSON K,SHAW G,LEUSCH F D,et al. Chlorine disinfection by-products in wastewater effluent:Bioassay-based assessment of toxicological impact[J].Water Research,2012,46(18):6069-6083.
[2] WANG X,WANG Y G,SUN C H,et al. Formation mechanism and assessment method for urban black and odorous water body:A review[J]. Chinese Journal of Applied Ecology,2016,27(4):1331-1340.
[3]付莹,赵玉蓉.氨氮对鱼类的毒性及鱼类应对氨氮毒性的策略[J].水产学杂志,2018,31(3):49-54.FU Ying,ZHAO Yurong.A review:toxicity of ammonia and detoxification of ammonia in fish[J]. Chinese Journal of Fisheries,2018,31(3):49-54.
[4] DU Y,WU Q Y,LU Y,et al. Increase of cytotoxicity during wastewater chlorination:Impact factors and surrogates[J]. Journal of Hazardous Materials,2017,324(Pt B):681-690.
[5]李承元.有色金属的性质和用途[J].有色金属科学与工程,1988(4):65-67.
[6]李洪桂.钨冶金学[M].长沙:中南大学出版社,2011:179-180.
[7]李会强,唐忠阳,何利华,等离子交换技术在钨冶金中的应用与进展[J].中国钨业,2014,29(5):34-39.LI Huiqiang,TANG Zhongyang,HE Lihua,et al. Applications and developments of ion exchange technology in tungsten metallurgy[J].China Tungsten Industry,2014,29(5):34-39.
[8]黄军,邵永康.高效吹脱法+折点氯化法处理高氨氮废水[J].水处理技术,2013,39(8):131-133.HUANG Jun,SHAO Yongkang.Treatment of the wastewater containing high NH3-N by high efficiency striping-breakpoint chlorination[J]. Technology of Water Treatment,2013,39(8):131-133.
[9]鲁秀国,罗军,赖祖明.氨氮废水处理技术发展现状[J].华东交通大学学报,2015(2):129-135.LU Xiuguo,LUO Jun,LAI Zuming.Development of ammonia nitrogen wastewater treatment technology[J]. Journal of East China Jiaotong University,2015(2):129-135.
[10]姚丽华,陈树茂,杨红.钨冶炼离子交换工艺废水的治理[J].湖南有色金属,2007,23(1):42-44.YAO Lihua,CHEN Shumao,YANG Hong. Treatment of waste water in ion exchange craft of wolfram smelting[J]. Hunan Nonferrous Metals,2007,23(1):42-44.
[11]刘莉峰,宿辉,李凤娟,等.氨氮废水处理技术研究进展[J].工业水处理,2014,34(11):13-17.LIU Lifeng,SU Hui,LI Fengjuan,et al. Research progress in the treatment technology of ammonia nitrogen wastewater[J]. Industrial Water Treatment,2014,34(11):13-17.
[12]黄海明,肖贤明,晏波.折点氯化处理低浓度氨氮废水[J].水处理技术,2008,34(8):63-65.HUANG Haiming,XIAO Xianming,YAN Bo. Experimental research on the treatment of low concentration ammonia nitrogen wastewater by breakpoint chlorination[J]. Technology of Water Treatment,2008,34(8):63-65.
[13] CORO E,LAHA S. Color removal in groundwater through the enhanced softening process[J]. Water Research,2001,35(7):1851-1854.
[14]黄慧婷,张明明,王敏,等.紫外/氯消毒在饮用水处理中的应用[J].净水技术,2018,37(10):44-48.HUANG Huiting,ZHANG Mingming,WANG Min,et al. Application of UV/chlorine disinfection in drinking water treatment[J].Water Purification Technology,2018,37(10):44-48.
[15] PRESSLEY T A,BISHOP D F,ROAN S G. Ammonia-nitrogen removal by breakpoint chlorination[J]. Environmental Science&Technology,1972,6(7):622-628.
[16]陈金銮,施汉昌,徐丽丽. pH值对氨氮电化学氧化产物与氧化途径的影响[J].环境科学,2008,29(8):2277-2281.CHEN Jinluan,SHI Hanchang XU Lili.Effect of p H for the electrochemical oxidation products and oxidation pathways of ammonia[J].Chinese Journal of Environmental Science,2008,29(8):2277-2281.
[17]孙锦宜.含氮废水处理技术与应用[M].化学工业出版社,2003:129-130.
[18] KIM K W,KIM Y J,KIM I T,et al. The electrolytic decomposition mechanism of ammonia to nitrogen at an IrO2 anode[J].Electrochimica Acta,2005,50(22):4356-4364.
[19] WATSON K,SHAW G,LEUSCH F D,et al. Chlorine disinfection by-products in wastewater effluent:Bioassay-based assessment of toxicological impact[J].Water Research,2012,46(18):6069-6083.